Plasticized halogen-containing resins



Patented Dec. 29, 1953 PLASTICIZED HALOGEN CON TAININ G RESIN S Joseph R. Darby, Richmond Heights, and Louis E. Wells, Jr., Webster Groves, Mo., assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application October 1, 1951, Serial No.249,214

14 Claims.

This invention relates to plasticized halogencontaining resin compositions exhibiting improved anti-blocking properties and improved lubricity. More particularly this invention relates to plasticized halogen-containing vinylidene resins exhibiting improved anti-blocking properties and improved lubricity.

The object of this invention is to provide a class of materials which may be manufactured at low cost and which when incorporated into a plasployed to improve the lubricity of resinous compositions are called lubricants.

It is well recognized in the art that materials, more specifically lubricants, which are primarily used to prevent sticking of resinous compositions, particularly halogen-containing resin compositions, to molds or the surfaces or nozzles of extrusion apparatus do not have the efiect of antiblocking materials in producing an anti-blocking action. In other words anti-blocking action is distinguished from a distinctly lubricating action.

It has been suggested in the art that certain esters of unsaturated fatty acids function as heat and light stabilizers for plasticized halogen-containing resins.

In accordance with this invention it has been discovered that a partial ester of the general formula where R and R" are like or unlike alkylene groups, where a: is an integer from 0 to and where ROO is the acyloxy group derived from a mixture of aliphatic and resin acids, when incorporated in small quantities in a plasticized halogen-containing resin composition. in addition to stabilizing the calendered or sheeted films to cohere or block when placed in contact and, further, prevents sticking of the halogen-containing resin composition to the metal surfaces of the molding or extrusion apparatus. R and R." may also contain hydroxyl groups.

This remarkable result is dependent upon the two diiierent acids being mixed prior to the formation of the partial ester, however, the reaction is not completely understood. If the partial esters of the two difierent acids are separately prepared and then mechanically mixed the unique effect is not produced.

The partial esters of this invention are prepared by several well-known methods. For example by reacting, in proper proportions, ethylene oxide, propylene oxide, trimethylene oxide, epichlorhydrin, glycerol chlorhydrin, ethylene glycol, trimethylene glycol, propylen glycol, diethylene glycol, triethylene glycol, glycerol, polyglycerol, and the like or mixtures thereof with a mixture of organic acids, at least one of which is a resin acid and the others are aliphatic or fatty acids.

A typical resin acid as described in this application is known as an abietic acid, the chemical constitution of which has been suggested as follows:

The preferred method of carrying out the present invention is to employ a partial ester of the general formula,

where R-C oand a: have the same significance as aforenoted. These esters are prepared by reacting the mixed acids with at least an equimolecular proportion of ethylene oxide. Th partial esters obtained by the reaction of the mixed acids with at least equimolecular proportions of alkylene oxides other than ethylene oxide such as propylene oxide, 1. e.,

etc., are also effective lubricants and anti-blocking agents.

Among the acid mixtures contemplated are the following:

i Alipfiatic acid V E plus l'icsin acid (1) Oleic acid Kbictic' acid (CiOHadOz) (2) Ste-aric acid Abietic acid (3) Stearic acid Pimaric acid (CzOHaOOi) (4) Laurie acid Abictic acid Palmitic acid limar-ic-acid (6) Oleic acid, stearic acid Ableticacid (7) Oleic acid, lauric acid Abictic acid (8) Stearic acid, oleic acid, lauric acid Abictic acid, pimaric acid 9) ivlyristic acid -Abietic acid (0) Ethyl hexoic acid 'Ahieticacid The mixture of organic acidsma'y contain' any number of difierent aliphatic fatty acids and the only limiting factor is that at least one-of the other acids shall be of the resin acid type. .Isomers of the respective aliphatic and resin acids may also be used. The aliphatic tattyacid and the resin acid may eachbe varied within limits 'so thalt each'aoidmay cornpr-ise 20 'to 80% or the total tr'ni-Xed acid. "The preferred 'alip'hatic fatty acids are those-containing 12-18 carbon It been further foundthata -cheap and plentiful source of a mixtu-redf aliphatic and resin"acidsare oils kno'wnas -tall oils. The tall oils vary'in"comp'osition,*for example the all-- Tphatic "fatty"a'ciiis in"'ifferent grades varying "from"-20% to 60% ancl'theresin acids'from to6'0'%. The balance or "materials consisting of sterols, "higher alcohols "and other constituents having little or no eifectfonthe process of this invention. such-talloils inay be used'as the raw "materials-in the preparation of the partial esters of this invention "or the aliphatic acid *or acids and the resin acid oracids rnay be mechanically i'r'iixedprionto" the formation of thepartial ester. To illustrate "the lubricity of a l halogen-contaiinirig resinponiposition containing a partial "estei'fofthis invention "the "beta-'hydroxy ethyl ste'rbf tall Oil where R-f) o is the acyloxy group derived from tall oil, is com- "p'oimded ina "plasticized poly-vinylchloride 00mpositioweinploying a difier'ential' speed two-roll "56 *None omi g not'beigt'u'oved from roll mi 50 l Regnoveable from roll mill at C. 50 2 Removahsmoothand facile at To illustrate the anti-blocking properties of a halogen-containing resin c'omposition'containing a partial ester ofthis invention the following compositions are prepared employing the same from the respective compositions.

manipulative procedure to obtain a homogeneous product:

'Filmspf about 0.020 inch in thickness are formed Two strips (1" by 6") are cut from the central portion of each film, pressed face to face between glass plates under a' 'pressure of 0.17 lb. per sq. in. (l

30 minutes while they are heated to a temperature of F. and are then allowed to cool to room temperature while under the aforesaid pressure. The glass plates are removed and the strips tested for surface cohesion by pulling the strips -a'pa'r t on ca :sc'ott tensile :tester. Zli'he cohesive force (averageiof :four tests) in pounds per inch for composition A is about 10 times that of compositionB and about15 times that of composition C. Cohesiveiiorce is the'force lbs.;,per inch width necessary to :pull. apart .th cohered surfaces of the strips.

lEmployingLthe following partial "esters is'the'acyloxy group *derivedfrom tall oil,respective1y,in' pla'ce ofthe beta hydroxy ethyl ester of 'a'dded'to "the halogemcontaining'resin at any resinf'althoug'h' it'isfpreferre'd to add them before heat'process'ing the "composition. They may conyenientIy'be addedby 'di's solvingin' the'plasticizer before adding "the latter to the resin. The amount oi"thejpartialesterof this invention employe'd m'ay vary widely and sti1l"produ'c'eim provemients in" lubricity andanti blocking .propertie's. Usually from 011 to" 5 by weight'on'the halogen-containing resin "is satisfactory, however, "amounts outside this range "maybe employed depending upon the particular'resin; other compounding-material's, and the results "desired. In general it'is preferred to employ '0.'5%"tof'2'% by weight based on the halogen-containing resin.

Although the par'tial esters of this invention are effective in halogen-containing resins incorporating any vofthe ordinaryplasticizers, the mostsatis-factory results are obtained with those plasticizers which are completely organic'in nature, such as dibutyl phthalate, dioctyl phthalate, butyl phthalyl butyl glycollate, dibutyl sebacate, and the like. Very satisfactory results are also obtained when-thepartial esters -otthis inven- 1 tion are used in coniunction-with the phosphate ester plasticizers such as. the well known -=alkyl diaryl' phosphates :in-which the .alkyl group contains -6l4:- carbonetomsfiand the arylgroupsaare phenyl or cresyl groups or mixtures thereof, e. g., 2-ethylhexyl-diphenyl phosphate, dodecyl dicresyl phosphate, tricresyl phosphate, etc. The amount of plasticizer which is used may be widely varied depending upon the particular plasticizer, the particular halogen-containing resin, and the particular use contemplated for the plasticized composition. Usually, however, from -100 parts of the plasticizer or mixture of plasticizers are used for every 100 parts of the halogen-containing resin.

Pigments, fillers, etc., which are commonly used in the plastic industries may be incorporated in the halogen-containing resins without destroying the anti-blocking or lubricity eiTect of the partial esters of this invention.

A halogen-containing resin composition particularly exhibiting th improved properties of this invention is one containing 25 to 40 parts dioctvl phthalate, to parts of a liouid partially hydro enated. mi ed isomeric terphenyl known as Hl3l0, and 0.5 to 2 parts of the beta hydroxy ethyl ester of tall oil for every 100 parts of a vinyl-chloride resin.

The halogen-containing resins of this invention are those derived from such vinylidene cornpounds as vinyl chloride, vinylidene chloride, vinyl chloracetate, chloro styrene, chlorobutadienes, etc. and those copolymers of such vinylidene co poun s and other unsaturated materials 00- polymerizab-le therewith, for example, copolymers of a vinylidene halide such as vinyl chloride with such materials as vinylidene chloride, vinyl esters of carboxylic acids, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; esters of unsaturated acids, for example, alkyl aorylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, allyl acrylate and the corresponding esters of methacrylic acid; vinyl aromatic compounds, for example styrene, ortho chloro styrene, para-chlorostyrene, 2,5- dichloro-styrene, ZA-dichloro-styrene, para-ethyl styrene, divinyl benzene, vinyl naphthalene, aloha-methyl styrene; dienes, such as butadiene, chlorobutadiene; unsaturated amides, such as acrylic acid amide, acrylic acid anilide; unsaturated nitril-es, such as acrylic acidnitrile; esters of a,b-unsaturated carboxylic acids, for example, the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl, and phenyl esters of maleic, crotonic, itaconic, fumaric acids and the like. The class of copolymers in which a predominant proportion, i. e., more than 50% by weight of copolymer is made from a halogencontaining vinylidene compound such as vinyl chloride, represents a preferred class of resins to be treated in accordance with this invention.

A particularly preferred embodiment of the invention comprises the improvement of lubricity and anti-blocking properties of resins prepared by c-opolymerizing vinyl chloride and an ester of an (Lb-unsaturated dicarboxylic acid such as diethyl maleate or other esters of maleic, fumaric, aconitic, itaconic acids, etc., in which 5-20 parts by weight of diethyl maleate or other analogous ester are used for every 95-80 parts by weight of vinyl chloride. Among the preferred esters of cub-unsaturated dicarboxylic acids are the alkyl esters in which the alkyl group contains 1-8 carbon atoms.

The partial esters of this invention are also effective in halogen-containing resins containing halogens other than chlorine, e. g., bromine, fluorine and iodine. The halogen-containing resins may contain a varying proportion of haloupon the weight of the resin of the beta-hydroxy ethyl ester of tall oil.

4. A composition comprising a vinyl chloride resin, di-octyl phthalate, a liquid partially hydrogenated mixed isomeric terphenyl, and 0.5% to 2% based upon the weight of the resin of the beta-hydroxy ethyl ester of tall oil.

5. A composition comprising a halogenated vinylidene polymer and a partial ester of the structural formula R( 1ORO-(RO),H Where R and R" are alkylene groups, where a: is an integer from 0 to 5, inclusive, and where o Rilerepresents the mixture of acyloxy groups obtained from tall oil by removal of the hydrogen atoms of the carboxyl groups of the mixture of acids of tall oil, which mixture of acids is represented by the structure 6. A composition comprising a plasticized chlorinated vinylidene polymer and a partial ester of the structural formula of tall oil, which mixture of acids is represented by the structure 7. A composition comprising a plasticized chlorinated vinylidene polymer and a partial ester of the structural formula tained from tall oil by removal of the hydrogen atoms of the carboxyl groups of the mixture of ama gam acids of tall oil, whioh m-ixtureof acids is repree sented by the structure ,{1 R co rf 8. A composition comprising a-p-last-ioized chlorinated vinylidene polymer containing: at least 50% by weight vinyl chloride and a partial ester of the structural formula R-tio-R'o- Womi where R and R are ethylene groupswhere a: s 2, and where 3, we'd-- represents the mixture of acyloxy groups obtained from tallo il by removal of the hydrogen atoms or" the oarboxyl groups of the mixture of acids of tall oilg which -mixtureof acids is repre sented by the structure 1? R con- 9. A composition comprising a halogenated vinylidene polymer and a preformed mixed partial ester of the structural formula (l? R-GO-E'O -(WOMZ-I where R and R" are alkylene groups, where a; is an integer from 0 to 5,inclusive, and where 0 M R-C orepresents the miitureof acyloxy" group's obtained from a mix tu-rebf acidsreprejsentedb'y the structure E l /OH by removal of the" hydrogen atoms of the carboxyl groups'of the mixture of acids, 20% to '80 by weight of said mixture: ofacids be'i'ng resiii acid and the balance being aliphatic fatty acids containing from 8 to 18 carbon atoms, inclusive, said preformedmixed' partial ester being prepared by reacting said mixture of-resin acid andaliphat'ic acid with an esterifyingagentcapable of introducing the -R'O -(R" C))I H grouping.

10. A composition comprising a plasticized chlorinated vinylidene polymer containing at least 50% by weight vinyl chloride and a preformed m i z'red partial ester" of the structural formula- \o\'l RGO-R'O.'-(R"O),H where" R and R" arealk'ylene groups,= where a: is'an-int'eger from 0 to 5, inclusive, and where o ll RCO- represents the mixture ofacyloxy groups obtained from a mixture of acids represented by thestructureif R con by removal of the hydrogen atoms of the caroxyrgrqups of the mixture of aoids,- 20% to 80% by weight or said mixture of acids being abietic acid and the balance being aliphatic fatty acids containing from 12 to 13 carbon atoms, inclusive saicl preformed mixed-partial ester bei'ng 'pi'e'pared by reacting said mixture of ab ietic acid and aliphatic acids with an esterifying agent capable of introducing the 'R-O=(R"O)eH grouping.

11. The composition of claim 10' which the piasticiaer is a phosphate ester plasticizer.

12. The'comp'ositio'n; of claim 10in which the plastio'izei' is an alkyl' dia'r'yl phosphate wherein the alkyl group contains 6-14 carbon atoms and the aryl radicals are'selecte'd'from the group consisting of phenyl' and cresyl radicals.

13. hecompositioii of claim 10 wherein the chlorinated vihylidene'polyriier is a vinyl chloride-Vinyl acetate opo1ymer'c'ontainingat least by weight vinyl chloride. I

1 4. Thecoin'position of claiin 10' wherein the chlorinated vinylidene' polymer is a vinyl chloride-diethy'l maleat copolyni'er in which at least by Weight isni'ade from vinyl chloride".

JOSEPH DARBY. LOUIS E. WELLS, JR.

References oitea in'thefile of this patent UNITED STATES PATENTS 

9. A COMPOSITION COMPRISING A HALOGENATED VINYLIDENE POLYMER AND A PREFORMED MIXED PARTIAL ESTER OF THE STRUCTURAL FORMULA 